CN102059093B - Arsenic and fluorine removing nano-composite adsorbent - Google Patents
Arsenic and fluorine removing nano-composite adsorbent Download PDFInfo
- Publication number
- CN102059093B CN102059093B CN200910223338A CN200910223338A CN102059093B CN 102059093 B CN102059093 B CN 102059093B CN 200910223338 A CN200910223338 A CN 200910223338A CN 200910223338 A CN200910223338 A CN 200910223338A CN 102059093 B CN102059093 B CN 102059093B
- Authority
- CN
- China
- Prior art keywords
- arsenic
- fluorine
- active carbon
- adsorbent
- adsorption
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention relates to a high-efficiency composite adsorbent TLA (Ti-La-AC) for simultaneously removing arsenic and fluorine from water. In the adsorbent, active carbon is used as a substrate, and titanium dioxide and lanthanum oxide are loaded on the substrate. Adsorption experiments show the TLA adsorbent has higher arsenic/fluorine adsorption capacity, and the arsenic removing performance is superior to that of active aluminum oxide and E33p (iron oxide). The adsorbent has a simple and practicable preparation process, stable adsorption performance and a high-efficiency adsorption process, is easy to operate, can also be recycled, and cannot cause secondary pollution to the environment.
Description
One, technical field under the present invention
Environmental science and technical field
Two, technical background of the present invention
The pollution of arsenic and fluorine with poison the problem that become international.As one of the most serious country of arsenic, fluoride pollution, the phenomenon of regional ubiquity High Concentration of Arsenic fluorine water coexistence such as Xinjiang of China, Shanxi, the Inner Mongol, Guizhou, and therefore cause arsenic fluorine associating poisoning to take place frequently.The National Standards Commission and the Ministry of Public Health unite the concentration of clearly having stipulated arsenic, fluorine in the drinking water in the issue " drinking water sanitary standard " (GB5749-2006) should be respectively less than 0.01mg/L and 1mg/L.
China mainly adopts water dispersion type in the rural area at present, because the less causes water treatment system configuration of water supply scale difficulty strengthens.In order to solve the drawback that existing way of supplying water exists, the water treatment technology that research and development are fit to rural community and family is extremely urgent.Absorption method is because its cost is lower, easy and simple to handle, treatment effect is good, has become the optimal selection of external small community and home treated high-fluorine water and high arsenic water.Absorption method adsorbent commonly used comprises activated alumina, active carbon, iron oxide and titanium oxide etc.Though iron oxide can arsenic removal in the above-mentioned sorbing material, and is extremely low to the removal efficient of fluorine; Active carbon and activated alumina can be used for the arsenic fluorine and remove altogether, but adsorption capacity is unsatisfactory.Therefore, synthetic adsorption efficiency height of development and reproducible arsenic fluorine remove composite adsorbing material altogether has significance.
Nano-TiO
2Sorbing material has high-adsorption-capacity (all greater than 37mg/g) to As (V) and As (III), and its arsenic removal performance is superior to activated alumina (Al
2O
3) (1.4～2.0mg/g) and E33p (iron oxide) (about 18.0mg/g).Meanwhile, TiO
2Can improve phreatic hardness, this can alleviate the threat that the rural area bitter brings to health to a certain extent.Other has bibliographical information TiO
2Clearance to fluorine can reach more than 90%.The lanthana stable performance, moderate cost, and can effectively remove the fluorine in the water.Recently existing research shows, after loading lanthana on adsorbent commonly used such as resin or the silica gel, can significantly improve the adsorption capacity of fluorine, this compound adsorbent long service life, and regeneration is simple, can not cause secondary pollution.As a kind of high-quality adsorbent, active carbon has unique pore structure and surface functional group, and its mechanical strength is high, and enough chemical stabilities are arranged, and can be acidproof, alkaline-resisting, heat-resisting.In water treatment procedure active carbon not only can deodorizing, taste removal, remove colourity; Can also remove OCPs (organo-chlorine pesticide), ABS organic pollutions such as (sodium alkyl benzene sulfonate, synthetic detergents), active carbon has become one of widely used water treatment absorbent at present.
This research is substrate with the active carbon, utilizes ultrasonic load method that titanium dioxide and lanthana are loaded into activated carbon surface, obtains a kind of fluorine of arsenic efficiently and removes nano adsorption material altogether.Through a series of experiments, studied the removal effect of this adsorbent to arsenic, fluorine.The present invention is intended to for the water treatment technology in China rural area a feasible scheme is provided, to ensure resident's drinking water safety.
Three, summary of the invention of the present invention
Illustrate main purpose of the present invention and characteristic of the present invention through following description.The arsenic fluorine that the present invention relates to removes compound adsorbent altogether, is to be substrate with the active carbon, the compound adsorbent that titanium dioxide of load certain amount of nano above that and lanthana obtain.
1 at first carries out preliminary treatment to active carbon, and the active carbon after sieving (20-60 order) is heated to boiling in deionized water, and this process keeps 30min, and the cooling back is with deionized water drip washing two to three times, in 104.5 ℃ of following dry for standby.
2 take by weighing a certain amount of titanium sulfate is dissolved in the deionized water, processes certain density titanium sulfate solution.To pass through pretreated active carbon and add by a certain percentage in the titanium sulfate solution, ultrasonic load some hrs, oven dry obtains product 1 under 104.5 ℃.
3 join product 1 in the certain density lanthanum nitrate hexahydrate in proportion, and ultrasonic load some hrs is in 104.5 ℃ of oven dry down.This step obtains product 2 after repeating for several times.
4 with product 2 in 200 ℃-600 ℃ roasting a period of times, promptly get the arsenic fluorine and remove compound adsorbent (hereinafter to be referred as TLA) altogether.
Four, description of drawings
The present invention is in the natural water of 5-8 at pH, has excellent arsenic, fluorine and removes performance altogether, and the saturated adsorption capacity of arsenic fluorine is respectively 37mg/g and 27mg/g.In order better to describe characteristic of the present invention, help explain the performance of adsorbent TLA in conjunction with following accompanying drawing.
Accompanying drawing 1 is stereoscan photograph and energy spectrum analysis figure after TLA difference arsenic-adsorbing of the present invention, the fluorine with Fig. 2; Through energy spectrum analysis; Can find out and contain elements such as carbon, titanium, lanthanum, oxygen on the adsorbent simultaneously, this for integrated application of the present invention the good absorption property of active carbon, titanium dioxide and lanthana precondition is provided.After adsorption reaction is accomplished, the characteristic peak of arsenic/fluorine has appearred in the adsorbent, and experimental result shows that TLA can be used for arsenic, fluorine is removed.
Accompanying drawing 3 is the X-ray diffractogram (XRPD) of TLA.Compare with active carbon, Detitanium-ore-type TiO occurred in the XRPD collection of illustrative plates of TLA
2Characteristic absorption peak, this further specifies titanium dioxide and is present among the TLA really.Do not have tangible La absworption peak in the spectrogram, explain that lanthanum possibly be present in the adsorbent with amorphous oxidation lanthanum.Compare with the lanthana of crystal habit, the lanthana of amorphous state has bigger specific area and Geng Duo adsorption site, therefore has stronger adsorption capacity.
Accompanying drawing 4 is TLA and arsenic commonly used, fluorine adsorbent E33P and Al
2O
3Absorption property relatively.Can find out that by Fig. 4 compare with other two kinds of adsorbents, adsorbent TLA of the present invention improves a lot to the adsorption efficiency of arsenic and fluorine.Wherein, TLA is 60%～80% to As (III) adsorption rate, and the best is preferably 68%; TLA is 70%～80% to As (V) adsorption rate, and the best is preferably 78%; TLA is 80%～90% to As (V) adsorption rate, and the best is preferably 86%.
Accompanying drawing 5 is curve of adsorption kinetics of TLA, and wherein scheming a is single arsenic list fluorine adsorption curve, figure b arsenic fluorine coexistence adsorption curve.Visible by figure; TLA gets final product balance and reaches maximum adsorption capacity the about 15min of the adsorption process of As and F; The arsenic maximal absorptive capacity is about 30mg/, the fluorine maximal absorptive capacity is about 10mg/L, absorption does not have very big difference under single arsenic list fluorine and arsenic fluorine coexistence different condition.Experimental result explanation adsorption reaction speed is fast, the superior performance of adsorbent.
Five, inventive embodiments
Further set forth the present invention below through embodiment.
Embodiment 1 Activated Carbon Pretreatment: 20～60 purpose active carbons are boiled 0.5h in ionized water, with after the deionized water drip washing in 104.5 ℃ of dry for standby.The load titanium: take by weighing the 7.5g titanium sulfate and be dissolved in the 40ml deionized water, 12g is joined above-mentioned solution through pretreated active carbon, ultrasonic load 4h gets product 1; Lanthanum-carried: as to take by weighing 2.5g La (NO
3)
36H
2O is dissolved in the 40ml deionized water, product 1 joined in this lanthanum nitrate hexahydrate, and ultrasonic load 4h, this step repeats twice and obtains product 2.Product 2 at 400 ℃ of following roasting 6h, is used washed with de-ionized water after cooling, and oven dry obtains end product TLA under 104.5 ℃.Verify through adsorption test: 2g adsorbent TLA is joined 40mL contains in the copper mine waste water of arsenic 7g L-1, fully mix 1h after, record that the residual volume of arsenic is merely 0.04mg L-1 in the solution.
Three kinds of adsorbents of table 1. are to the clearance of arsenic and fluorine
The foregoing description explanation, building-up process of the present invention is simple and easy to do, compares with adsorbent commonly used at present, and TLA adsorbent of the present invention is high to the removal efficient of arsenic and fluorine, and it is very obvious that the arsenic fluorine removes effect altogether.
Claims (2)
1. an arsenic fluorine removes nano-compound adsorbent altogether, and it is characterized in that: this compound adsorbent is composited by titanium dioxide, lanthana and active carbon, can be simultaneously arsenic removal defluorination efficiently; The preparation method of said compound adsorbent is: the titanium sulfate solution of putting into pretreated active carbon in proportion 187.5g/L earlier; Ultrasonic load 4 hours; 104.5 ℃ of dry down loads of accomplishing a titanium, put into the lanthanum nitrate hexahydrate of 46.65g/L again, ultrasonic load 4 hours; Dry down at 104.5 ℃; This step repeats the load of twice completion lanthanum, obtains end product arsenic fluorine at 300 ℃ of following roasting 6h at last and removes compound adsorbent altogether, and wherein the mass ratio of titanium sulfate, lanthanum nitrate, active carbon is 0.625: 0.21: 1.
2. arsenic fluorine as claimed in claim 1 removes nano-compound adsorbent altogether; Said active carbon is as substrate, and its processing method is: select 20-60 order granular active carbon for use, boil 30min with deionized water; Use twice of deionized water drip washing or three times then, 104.5 ℃ of oven dry down.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910223338A CN102059093B (en) | 2009-11-18 | 2009-11-18 | Arsenic and fluorine removing nano-composite adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910223338A CN102059093B (en) | 2009-11-18 | 2009-11-18 | Arsenic and fluorine removing nano-composite adsorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102059093A CN102059093A (en) | 2011-05-18 |
| CN102059093B true CN102059093B (en) | 2012-10-10 |
Family
ID=43994706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910223338A Active CN102059093B (en) | 2009-11-18 | 2009-11-18 | Arsenic and fluorine removing nano-composite adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102059093B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103238723B (en) * | 2012-02-10 | 2014-10-29 | 上海市水产研究所 | Preparation method of low-fluorine euphausia superb hydrolyzed protein powder |
| CN102886239A (en) * | 2012-09-13 | 2013-01-23 | 清华大学 | Method for preparing iron-titanium oxide serving as defluorination adsorbent |
| CN103752268B (en) * | 2014-01-16 | 2015-11-18 | 广东工业大学 | The filter core preparation method and application of heavy metal and arsenic, fluorine in absorption drinking water |
| US9901918B2 (en) * | 2015-03-04 | 2018-02-27 | Graver Technologies Llc | Hybrid ion exchange material and method for making the same |
| CN105123758B (en) * | 2015-09-08 | 2018-07-06 | 福州麦克纳诺生物科技有限公司 | A kind of nanometer of bamboo vinegar is as the application in plant growth regulator |
| CN105217714B (en) * | 2015-09-19 | 2017-12-29 | 中国科学院生态环境研究中心 | A kind of titanium aluminium composite sphere adsorbent for drink water purifying |
| CN105344316A (en) * | 2015-10-30 | 2016-02-24 | 明光市龙腾矿物有限公司 | Composite material prepared from active carbon and used for adsorption, and preparation method thereof |
| CN105344317A (en) * | 2015-10-30 | 2016-02-24 | 安徽炭之馨环保科技有限公司 | Active carbon stain remover |
| CN105664839B (en) * | 2016-03-30 | 2018-04-06 | 中国科学院生态环境研究中心 | One kind carries lanthanum titanium dioxide arsenic fluorine altogether except sorbing material and preparation method thereof |
| CN106914220A (en) * | 2017-04-10 | 2017-07-04 | 河南永泽环境科技有限公司 | A kind of modified turf fluorine removal medicament and preparation method thereof |
| CN107198934A (en) * | 2017-07-18 | 2017-09-26 | 西安鼎研科技股份有限公司 | A kind of VOCs administering method of water using crystalline state as adsorbent |
| CN107746073B (en) * | 2017-10-10 | 2020-06-23 | 中国科学院生态环境研究中心 | Preparation method of granular titanium dioxide and lanthanum-loaded granular titanium dioxide |
| CN108993382B (en) * | 2018-06-25 | 2021-09-07 | 湖南烯富环保科技有限公司 | Defluorination material based on mushroom dregs and regeneration method thereof |
| CN108993391A (en) * | 2018-08-14 | 2018-12-14 | 长沙华盛新材料科技有限责任公司 | A kind of fluorine adsorbent and from fluorinated water removing recycling fluorine method |
| CN110947362B (en) * | 2019-11-27 | 2022-05-17 | 南通大学 | Ternary modified biochar for removing fluorine in water and preparation method thereof |
| CN114262646B (en) * | 2021-12-28 | 2024-04-16 | 山东中大药业有限公司 | Detergent for removing pesticide residues of traditional Chinese medicine plants and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323872A (en) * | 2000-05-17 | 2001-11-28 | 中国科学院大连化学物理研究所 | Dearsenicating catalyst |
| CN1417292A (en) * | 2001-11-06 | 2003-05-14 | 中国科学院大连化学物理研究所 | Catalyst for preparing alkane of diesel oil fraction from synthetic gas and its prepn |
| EP1847318A2 (en) * | 2006-04-18 | 2007-10-24 | Blücher GmbH | Board materials provided with adsorbents for dry construction |
| CN101537351A (en) * | 2008-03-21 | 2009-09-23 | 北京合创同盛科技有限公司 | Catalyst for catalytic combustion |
-
2009
- 2009-11-18 CN CN200910223338A patent/CN102059093B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323872A (en) * | 2000-05-17 | 2001-11-28 | 中国科学院大连化学物理研究所 | Dearsenicating catalyst |
| CN1417292A (en) * | 2001-11-06 | 2003-05-14 | 中国科学院大连化学物理研究所 | Catalyst for preparing alkane of diesel oil fraction from synthetic gas and its prepn |
| EP1847318A2 (en) * | 2006-04-18 | 2007-10-24 | Blücher GmbH | Board materials provided with adsorbents for dry construction |
| CN101537351A (en) * | 2008-03-21 | 2009-09-23 | 北京合创同盛科技有限公司 | Catalyst for catalytic combustion |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102059093A (en) | 2011-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102059093B (en) | Arsenic and fluorine removing nano-composite adsorbent | |
| CN104525119B (en) | A kind of g-C3n4functional charcoal sorbing material of/ZnO/ activated carbon and preparation method thereof | |
| CN103739043B (en) | A kind of granule electrode of photochemical catalysis three-dimensional electrode/electro-Fenton system and preparation method | |
| CN102921384B (en) | Method for preparing high-efficiency fluorine removal agent from solid wastes | |
| CN104549526B (en) | Metallic oxide/Cu2O/polypyrrole three-layer-structure hollow nanosphere and preparation method and application thereof | |
| CN109513424A (en) | A kind of carbon/hydrotalcite compound adsorbent and its preparation, application and regeneration method in heavy metal adsorption | |
| CN102502621A (en) | Post-treatment process for preparing super-capacitor active carbon with super-low ash content | |
| CN105481063B (en) | It is a kind of to be used to handle granule electrode of organic wastewater with difficult degradation thereby and preparation method thereof | |
| CN102247802A (en) | Method for preparing activated carbon | |
| Shi et al. | Hierarchically porous biochar synthesized with CaCO3 template for efficient Hg0 adsorption from flue gas | |
| CN104925913A (en) | Catalytic particle electrode used for removing refractory organics and ammonia nitrogen from wastewater and preparation method and application thereof | |
| CN105618066B (en) | A kind of catalytic wet oxidation catalyst and preparation method thereof | |
| CN102701201A (en) | Method for preparing activated carbon powder with lignin from alkaline papermaking black liquor | |
| CN103482624B (en) | Preparation method for active carbon with photocatalysis function | |
| CN102614854A (en) | Method for preparaing dephosphorized and ferrum-carried activated carbon adsorbent | |
| CN106732640A (en) | A kind of preparation method of the ozone decomposition catalyst web plate with modified meerschaum as carrier | |
| CN102078803A (en) | Regenerating unit for zeolite with ammonia-nitrogen saturation and application thereof | |
| CN105056884A (en) | Preparation method for activated carbon material for drinking water purification | |
| CN109289917A (en) | Alkali modification removes the preparation method of formaldehyde composite catalyst | |
| Huang et al. | Tailored high mesoporous activated carbons derived from Lotus seed shell using one-step ZnCl 2-activated method with its high Pb (II) capturing capacity | |
| CN102442664A (en) | Production method for bamboo electric double layer capacitor electrode active carbon | |
| CN101862644A (en) | Preparation method of Al-doped hydroxyapatite high-efficiency defluorinating adsorbent | |
| CN105709737B (en) | Catalytic wet oxidation catalyst and its preparation method | |
| CN102008938A (en) | Naphtha denitrification adsorbent and preparation method thereof | |
| CN102234145A (en) | Preparation method of fluoride removal electro adsorption electrode for drinking water and fluoride removal electro adsorption electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20171117 Address after: 710077 Shaanxi city of Xi'an province high tech Zone of Mocha hi tech road is 85 feet Patentee after: Xi'an Yi Tai environmental protection Limited by Share Ltd VIP Address before: 100085 Beijing city Haidian District Shuangqing Road No. 18 Patentee before: Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences |
|
| TR01 | Transfer of patent right |